用间接法测定硫化物的研究

前人已经报道用汞的冷原子吸收法测定硫化物,利用Hg~(2+)和S~(2-)形成很稳定的化合物,使汞的吸光度值降低,根据其降低的程度来测定硫化物的含量。这种方法简便、灵敏,但对加入的Hg~(2+)量有较大的限制。S_2O_3~(2-)、CN~-、I~-等也有严重干扰,这些离子常与S~(2-)共存于水样中,所以,实际测定时,常需分离这些离子。     

Rapid determination of total mercury in treated waste water by cold vapor atomic absorption spectrometry in alkaline medium with sodium hypochlorite solution

Addition of a sodium hypochlorite solution (9.2% (w/v)) was effective to reduce a sulfide interference in determination of organic mercury, including methylmercury and phenylmercury, as well as a previously reported determination of inorganic mercury by cold vapor atomic absorption spectrometry (CVAAS) in an alkaline medium. Total mercury ranging from 0.17 to 33 μg L⁻¹ in 15 mL of sample solutions containing up to 200 mg L⁻¹ of sulfide can be determined without any serious interference by sulfide when 1 mL of the sodium hypochlorite solution was added after dilution of the sample solution to 25 mL. The proposed method was simple and rapid because no digestion processes were required for the determination of total mercury; the time required for the determination was only about 5 min. The proposed method was applicable to the analysis of treated waste water.     

Direct measurement of the mercury content of exhaled air: a new approach for determination of the mercury dose received

A new rapid technique is presented for determination of the dose of mercury inhaled; it is based on direct measurement of the concentration of mercury in exhaled air by use of a Zeeman mercury spectrometer RA-915+. It has been demonstrated experimentally that the dose received during short-term exposure to mercury vapor is determined more reliably by this method rather than by conventional techniques based on measurement of the mercury content in blood or urine.     

Effet de L'irradiation a 253. 7 NM De La Vapeur du Mercure

Abstract

The mercury concentration in a clean, evacuated quartz vessel remains unchanged upon irradiation with the 253. 7 nm resonance line at room temperature. The observations of Shimomura et al and Slevin et al, can be explained by the reaction of electronically excited mercury with traces of oxygen and water vapor to give mercuric oxide.     

Elimination of sulfide interference by sodium hypochlorite solution in the cold vapor atomic absorption spectrometric determination of mercury using tin(II) reduction in alkaline medium

An addition of sodium hypochlorite solution effectively eliminated the interference by sulfide in the cold vapor atomic absorption spectrometric determination of mercury using tin(II) reduction in alkaline medium. Mercury ranging from 0.01 to 0.5 μg could be determined within ±10% error in 100 mL of sample solution containing 10 mg of sulfide by the addition of 1 mL of 10.4%(w/v) sodium hypochlorite solution. The proposed method is rapid (5 min per determination) and has good reproducibility (3.0%).     

Behavior of Mercury Vapor Upon Irradiation by a Mercury Lamp in an Inert Gas

Abstract

The behavior of mercury vapor during irradiation by a mercury lamp is investigated. Using the flameless atomic absorption technique for mercury determination, it was found that when mercury vapor in an inert gas is irradiated by a mercury lamp, the atomic absorption signal of mercury is decreased rapidly and the signal may be restored by heating to 70°C. These phenomena indicate that the irradiation products of mercury vapor in the quartz tube are deposited on the tube, and are dissociated into the mono-atomic state of mercury upon heating.     

聚苯胺及其复合物对重金属离子的高效吸附性能

基于国外最新文献,系统总结了近年来聚苯胺及其复合物的制备方法及其重金属离子吸附性能,重点分析了吸附性能特征,指出聚苯胺及其复合物具有吸附下限浓度低、达到吸附平衡快以及解吸附性能优异等特点.填充有聚苯胺颗粒的吸附柱在动态处理初始浓度为83 ng/L的汞离子溶液时,经一次吸附与解吸循环操作后,汞离子的富集倍数可达120倍.应用于冷原子吸收光谱的待测样品的浓缩与富集,可以将汞的测试下限拓展到0.05 ng/L.聚苯胺及其复合物在痕量重金属离子的高效富集与灵敏探测等方面展示了广阔的应用前景.     

A non-distillation kjeldahl method for nitrogen based on precipitation as tetraphenylborate

A simple, accurate method for the determination of protein nitrogen by a modification of the Kjeldahl procedure, eliminating the distillation step and weighing ammonium tetraphenylborate (TPB) precipitate directly, is described. The gravimetric factor is favorable, and no standard solutions are required. Interference from mercury catalyst was prevented by conversion to the soluble tetraiodomercurate(II) complex (method 1), removal of the tetraiodomercurate via anion-exchange resin (method 2), or removal of mercury as mercuric sulfide (method 3). Thusc 3 TPB Methods gave rusults as accurate and precise as the usual distillation approach. Values by method 1, averaged 100.5% recovery with a standard deviation of 1.8 ; and by method 2, which is used when large concentrations of mercury are present, they averaged 100.4% with 1.8 std. dev.     

Elimination of sulfide interference by sodium hypochlorite solution in the cold vapor atomic absorption spectrometric determination of mercury using tin(II) reduction in alkaline medium

An addition of sodium hypochlorite solution effectively eliminated the interference by sulfide in the cold vapor atomic absorption spectrometric determination of mercury using tin(II) reduction in alkaline medium. Mercury ranging from 0.01 to 0.5 μg could be determined within ±10% error in 100 mL of sample solution containing 10 mg of sulfide by the addition of 1 mL of 10.4%(w/v) sodium hypochlorite solution. The proposed method is rapid (5 min per determination) and has good reproducibility (3.0%). Received: 20 May 1998 / Revised: 7 July 1998 / Accepted: 10 July 1998     

Indirect Determination of Sulfide by Cold Vapor Atomic Absorption Spectrometry

A method for the determination of sulfide based on its interference with the determination of Hg by cold vapor atomic absorption spectrometry is described. The decrease in mercury absorbance at 253.7nm is proportional to the concentration of sulfide over the range of 10–320ngmL^–1. The limit of detection was found to be 7ngmL^–1 and the relative standard deviation (R.S.D.) for the determination of different concentrations of sulfide was in the range of 1.8–2.2%. This method was applied to the determination of sulfide in whole human blood after gas-phase separation.     

A low-cost non instrumental method for semiquantitative determination of mercury in fish

A non instrumental method for the semiquantitative determination of mercury in fish is described. The sample is acid digested and the mercury vapor released after chemical reduction with SnCl2. The mercury vapor is then collected on a detecting paper covered with an emulsion of Cu2I2, 3% carboxymethylcellulose and MgCl2 as moistener agent. The colored Cu2[HgI4] complex is formed and the color intensity is proportional to the mercury concentration in the original sample. Parameters such as sample mass/digestion solution volume ratio, emulsion composition, paper covering technique, carrier gas flow were investigated. Comparative studies using CVAAS and digital color analysis after scanning the papers confirmed the applicability of the method to real samples.     

Direct determination of mercury in cosmetic samples by isotope dilution inductively coupled plasma mass spectrometry after dissolution with formic acid

A new method was proposed for the accurate determination of mercury in cosmetic samples based on isotopic dilution (ID)-photochemical vapor generation (PVG)-inductively coupled plasma mass spectrometry (ICP MS) measurement. Cosmetic samples were directly dissolved in formic acid solution and subsequently subjected to PVG for the reduction of mercury into vapor species following by ICP MS detection. Therefore, the risks of analyte contamination and loss were avoided. Highly enriched ²⁰¹Hg isotopic spike is added to cosmetics and the isotope ratios of ²⁰¹Hg/²⁰²Hg were measured for the quantitation of mercury. With ID calibration, the influences originating from sample matrixes for the determination of mercury in cosmetic samples have been efficiently eliminated. The effects of several experimental parameters, such as the concentration of the formic acid, and the flow rates of carrier gas and sample were investigated. The method provided good reproducibility and the detection limits were found to be 0.6 pg mL⁻¹. Finally, the developed method was successfully applied for the determination of mercury in six cosmetic samples and a spike test was performed to verify the accuracy of the method.     

METHYLMERCURY: PHOTOCHEMICAL TRANSFORMATION OF MERCURIC SULFIDE INTO METHYLMERCURY IN AQUEOUS SOLUTIONS1

Abstract. The photochemical reaction of mercuric sulfide was studied in aqueous solutions. The photo-solubilization of mercuric sulfide occurred under irradiation with light of ≤650nm and was enhanced in the presence of oxygen and electrolytes. The resultant mercuric ions were easily methylated in the presence of acetate ions via the photosensitized reaction by the simultaneously produced "photo-sulfur" under irradiation with light of ≤420nm. The photoelectrochemical studies of mercuric sulfide electrode revealed that black mercuric sulfide was an n -type semiconductor and the photo-current due to the dissolution as mercuric ions was observed on anodic polarization. The photo-solubilization of mercuric sulfide may be interpreted in terms of the local-cell mechanism.     

Voltammetric Determination of Mercury(II) at Poly(3‐hexylthiophene) Film Electrode. Effect of Halide Ions

The well‐known method for the determination of mercury(II), which is based on the anodic stripping voltammetry of mercury(II), has been adapted for applications at the thin film poly(3‐hexylthiophene) polymer electrode. Halide ions have been found to increase the sensitivity of the mercury response and shift it more positive potentials. This behavior is explained by formation of mercuric halide which can be easily deposited and stripped from the polymer electrode surface. The procedure was optimized for mercury determination. For 120 s accumulation time, detection limit of 5 ng mL^?1 mercury(II) has been observed. The relative standard deviation is 1.3% at 40 ng mL^?1 mercury(II). The performance of the polymer film studied in this work was evaluated in the presence of surfactants and some potential interfering metal ions such as cadmium, lead, copper and nickel.     

A comparative study of radioactivation,atomic absorption and spectrophotometric techniques applied to the determination of mercury in lead

A fairly simple radiometric method has been developed for the quantitation of microgram amounts of mercury in lead samples of different purity grades. It is mainly based on 3 steps; (i) the removal of most interfering cations with ferric hydroxide scavenger in the presence of a suitable masking agent, (ii) the separation of mercury as hydrated mercuric oxide from a highly alkaline medium, (iii) its distillation as mercuric chloride followed by precipitation as the sulfide. The method is reproducible and the results which show, in general, a standard deviation of ±4.29% are compared with those obtained by atomic absorption (4.48%) and spectrophotometric (13.13%) techniques.     

Solution cathode glow discharge induced vapor generation of mercury and its application to mercury speciation by high performance liquid chromatography-atomic fluorescence spectrometry

A novel solution cathode glow discharge (SCGD) induced vapor generation was developed as interface to on-line couple high-performance liquid chromatography (HPLC) with atomic fluorescence spectrometry (AFS) for the speciation of inorganic mercury (Hg(2+)), methyl-mercury (MeHg) and ethyl-mercury (EtHg). The decomposition of organic mercury species and the reduction of Hg(2+) could be completed in one step with this proposed SCGD induced vapor generation system. The vapor generation is extremely rapid and therefore is easy to couple with flow injection (FI) and HPLC. Compared with the conventional HPLC-CV-AFS hyphenated systems, the proposed HPLC-SCGD-AFS system is very simple in operation and eliminates auxiliary redox reagents. Parameters influencing mercury determination were optimized, such as concentration of formic acid, discharge current and argon flow rate. The method detection limits for HPLC-SCGD-AFS system were 0.67 μg L(-1) for Hg(2+), 0.55 μg L(-1) for MeHg and 1.19 μg L(-1) for EtHg, respectively. The developed method was validated by determination of certified reference material (GBW 10029, tuna fish) and was further applied for the determination of mercury in biological samples.     

The heterometric microdetermination of mercury with mercaptobenzthiazole in the presence of an excess of foreign metals

1. A general method is presented for the determination of 1–2 mg mercuric mercury, in the absence of complexing agents, in 20 ml solution, with an error of 0–3 %. The solution may contain: Ca, Ba, Mg, Zn, Mn, Ni, Co or Cd as nitrate of sulphate in a concentration of 0.2M. The concentration of Pb should be <0.1M and that of Al, Cr or Fe ?0.05M. 2. A special method is presented for the determination of mercury (1–2 mg Hg in 20 ml) in the presence of large excesses of bismuth (?98%) by using ethylendiammetetraacetate. Error 0–3 %. 3. A method is presented for the determination of mercury in excesses of copper in an acetic acid solution which contains ethylendiaminetetraacetate. 4. A special method is presented which permits the determination of 1–2 mg mercury in 30 ml solution which contains large excesses of copper (up to 98% or more). The titration is carried out in an alkaline solution of trisodiumcitrate. The titration proceeds rapidly. Error 0–2%.     

Behavior of mercury(II) salts in electrothermal atomic absorption spectrometry : Application to the Determination of Thiosulfate

Mercury(II) salts have different decomposition temperatures in a graphite tube or tantalum coil used for electrothermal atomic absorption spectrometry. The nitrate, perchlorate and acetate were spontaneously reduced to mercury vapor at room temperature, but the thiosulfate, sulfide, cyanide and bromide were reduced only on heating. Chloride and thiocyanate in a graphite furnace and iodide in a tantalum coil did not give mercury absorbance on heating. Thiosulfate (1–10 × 10^?6 M) was determined by addition to mercury(II) nitrate in acetate buffer, removing the response from the excess mercury(II) nitrate by drying below 100° C in the graphite furnace, and measuring the mercury absorbance on heating, which was proportional to the thiosulfate concentration.     

Metal components analysis of metallothionein-III in the brain sections of metallothionein-I and metallothionein-II null mice exposed to mercury vapor with HPLC/ICP-MS

Mercury vapor is effectively absorbed via inhalation and easily passes through the blood–brain barrier; therefore, mercury poisoning with primarily central nervous system symptoms occurs. Metallothionein (MT) is a cysteine-rich metal-binding protein and plays a protective role in heavy-metal poisoning and it is associated with the metabolism of trace elements. Two MT isoforms, MT-I and MT-II, are expressed coordinately in all mammalian tissues, whereas MT-III is a brain-specific member of the MT family. MT-III binds zinc and copper physiologically and is seemed to have important neurophysiological and neuromodulatory functions. The MT functions and metal components of MTs in the brain after mercury vapor exposure are of much interest; however, until now they have not been fully examined. In this study, the influences of the lack of MT-I and MT-II on mercury accumulation in the brain and the changes of zinc and copper concentrations and metal components of MTs were examined after mercury vapor exposure by using MT-I, II null mice and 129/Sv (wild-type) mice as experimental animals. MT-I, II null mice and wild-type mice were exposed to mercury vapor or an air stream for 2 h and were killed 24 h later. The brain was dissected into the cerebral cortex, the cerebellum, and the hippocampus. The concentrations of mercury in each brain section were determined by cold vapor atomic absorption spectrometry. The concentrations of mercury, copper, and zinc in each brain section were determined by inductively coupled plasma mass spectrometry (ICP-MS). The mercury accumulated in brains after mercury vapor exposure for MT-I, II null mice and wild-type mice. The mercury levels of MT-I, II null mice in each brain section were significantly higher than those of wild-type mice after mercury vapor exposure. A significant change of zinc concentrations with the following mercury vapor exposure for MT-I, II null mice was observed only in the cerebellum analyzed by two-way analysis of variance. As for zinc, the copper concentrations only changed significantly in the cerebellum. Metal components of metal-binding proteins of soluble fractions in the brain sections were analyzed by size-exclusion high-performance liquid chromatography (HPLC) connected with ICP-MS. From the results of HPLC/ICP-MS analyses, it was concluded that the mercury components of MT-III and high molecular weight metal-binding proteins in the cerebellum of MT-I, II null mice were much higher than those of wild-type mice. It was suggested that MT-III is associated with the storage of mercury in conditions lacking MT-I, and MT-II. It was also suggested that the physiological role of MT-III and some kind of high molecular weight proteins might be impaired by exposure to mercury vapor and lack of MT-I and MT-II.     

Compositional analysis of American southwestern ceramics by neutron activation analysis

Mercury, a known neurotoxin, has been implicated in the etiology and pathogenesis of such disease states as Alzheimer's and Parkinson's diseases. There is concern that the exposure to mercury vapor released from dental amalgam restorations is a potential health hazard. Measurement of mercury concentrations in blood or urine may be useful in diagnosis of mercury poisoning and in assessing the extent of exposure. This study describes the optimization of pre-neutron activation analysis procedures such as sampling, selection of irradiation and counting vials and acid digestion in order to minimize mercury loss via volatilization and/or permeation through containers. Therefore, the determination of mercury can be complicated by these potential losses. In the optimized procedure 20 mL of urine was spiked with three different concentrations of mercury, digested with concentrated nitric acid, and placed in polypropylene vials for irradiation and counting. Analysis was performed by subtracting the Se-75 photopeak contribution to the 279 keV Hg-203 photopeak and applying the method of standard additions. Urinary mercury concentrations in normal human subjects were determined to be of the order of 10 ng/mL.